title: Electron attachment to POCl3. III. Measurement and kinetic modeling of branching fractions.
abstract: Electron attachment to POCl(3) was studied in the bath gas He over the pressure range 0.4-3.1 Torr and the temperature range 300-1210 K. Branching fractions of POCl(3)(-), POCl(2)(-), Cl(-), and Cl(2)(-) were measured. The results are analyzed by kinetic modeling, using electron attachment theory for the characterization of the nonthermal energy distribution of the excited POCl(3)(-∗) anions formed and chemical activation-type unimolecular rate theory for the subsequent competition between collisional stabilization of POCl(3)(-∗) and its dissociation to various dissociation products. Primary and secondary dissociations and∕or thermal dissociations of the anions are identified. The measured branching fractions are found to be consistent with the modeling results based on molecular parameters obtained from quantum-chemical calculations.
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Bedford, Massachusetts 01731-3010, USA.
authors.forename: Nicholas S
authors.initials: NS
authors.lastname: Shuman
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Miller
authors.forename: A A
authors.initials: AA
authors.lastname: Viggiano
authors.forename: Jürgen
authors.initials: J
authors.lastname: Troe
mesh_terms: D004583:Electrons; D006371:Helium / Q000737:chemistry; D007700:Kinetics; D017553:Phosphorus Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D017553:Phosphorus Compounds; D006371:Helium